DE570951C - Process for the manufacture of valuable liquid products from solid carbonaceous materials - Google Patents

Description

A process for the preparation of valuable liquid products from solid carbonaceous materials, it is already known to produce valuable liquid products by fixed, treated with 01 being pasted carbonaceous materials with hydrogen under pressure at elevated temperature in the presence of catalysts. In order to increase the yield, it has already been proposed to impregnate the solid starting materials with catalytically active material.

In such processes, too, the catalyst is already in the form a suspension 'in C) 1 or the coal-oil suspension serving as the starting material mixed in.

It has now been found that particularly high yields are obtained, if before the preparation of the mixture of oils to be subjected to the reaction with the solid starting materials and the latter are impregnated with catalytically active material or sprinkled as well as the former are mixed with catalysts.

Coal, peat, wood and the like can be used as solid starting materials. These are either granulated or finely ground in the dried or raw state used. For extensive removal of the ashes one can e.g. B. finely ground coal a flotation, sieving or a separation process due to the different subject to specific weights. The solid starting material is then mixed with a solution or fine suspension of the catalyst, e.g. B. a solution of a catalytically active Salt of the metals of the 2nd to the B. group sprinkled or soaked, with also increased Pressure, e.g. B. 5, 2o, 5o at or more, is applicable. As suitable catalyst solutions be z. B. called aqueous solutions of ammonium molybdate, ammonium tungstate or of Sulphosalts of molybdenum, tungsten, vanadium, tin, arsenic, antimony, copper, Rhenium, in particular of ammonium sulfomolybdate or ammonium sulfotungstate, also tin oxalate dissolved in ammonium oxalate solution or molybdenum heptachloride, molybdic acid chloride, tungsten hexachloride dissolved in naphthenic acid or in oleic acid or in coal liquefaction products, furthermore the aqueous solutions of nitrates, chlorides, phosphates of other metals.

As C51 for the preparation of the mixture, e.g. the carbon paste, one can use high-boiling fractions of crude oils, tars and hydrogenation products, expediently boiling above 325 ° or use middle oils or mixtures of these. Recommended as particularly beneficial themselves a mixture of medium oil with heavy oil in the ratio i: z. But you can also wholly or partially lower-boiling fractions, such as gasoline u. Like., Use, which evaporate after entering the reaction furnace.

The catalysts to be added to the oil are expediently finer Distribution used e.g. B. Metals of the 2nd to B. group or their oxides, sulfides, Carbonates, wherein the catalytically active material, e.g. B. ammonium molybdate, ammonium tungstate, ammonium sulfotungstate etc., can be arranged on carriers. As such come Florida earth, bauxite, pottery shards, active coal and the like in question. For example, those equipped with catalysts are used Finely ground carrier added to the oil.

The catalysts to be added to the two starting materials can thereby to be different.

The ratio of the solid starting materials to the oils is appropriate i: i. In this way with catalysts. provided mixture is then put together heated to reaction temperature with hydrogen and fed to the reaction furnace.

Due to the good distribution of the catalyst in the to be hydrogenated The highest possible yield is good in the procedure described above Liquefaction products achieved. Example i Ruhr coal is finely ground and soaked with a solution of ammonium molybdate, so that the carbon o, i ° / ° molybdic acid absorbs, and then dried. One obtained by pressure hydrogenation of the same coal Oil that boils above 325 ° and contains 4 ° / ° asphalt is given as much of a fine one ground catalyst, consisting of Florida earth soaked with ammonium molybdate solution to that the amount of molybdic acid in the oil is 0.1% based on coal.

The coal and oil are now mixed in a ratio of 4: 1 and put in an autoclave on plate-shaped inserts with a layer height of 2 to 3 mm arranged. The autoclave is opened under a hydrogen pressure of 25o at of a lead bath quickly to 370 °, then gradually over the course of an hour to 46o ° heated. This temperature is maintained for about 3 hours, with the hydrogen is passed continuously through the reaction chamber. 931 /, the carbon of the Coal are converted into liquid hydrocarbons containing z.5% asphalt. The non-liquefied part contains 6.6 parts of hydrogen per 100 parts of carbon.

Will the coal in the manner indicated above with the indicated amount soaked in a catalytic substance, but no catalyst is added to the oil only go ° / ° of the carbon is converted into liquid products. These contain 5 ° / ° Asphalt. The non-liquefied coal residue has 5.2 parts of hydrogen 100 parts of carbon.

Will only add the above-mentioned catalyst to the oil in the same amount added and the charcoal not impregnated, the conversion of solid matter is in liquid products only 84 ° / °. The liquefaction products contain 60/0 asphalt, the remaining carbon contains 6 parts hydrogen per 100 parts carbon.

About the same results are obtained when using the catalyst-free Coal-01 mixture corresponding amounts of the finely divided catalyst mentioned clogs. Example e. Ruhr coal with g0 / 0 ash components is processed in a cross beater mill ground to a grain size below 5 mm and then ground in one The windsifter freed from the coal dust with a grain size below 0.25 mm having. The ground material is then treated with a calcium chloride solution of the specific Weight 1.3 stirred. The ash components settle on the bottom of the Vessel while the carbon collects on the surface of the aqueous solution. The charcoal is separated off, washed with water and dried. The treated like that Coal contains only 1% / ° ash constituents, and the remaining part consists of go ° / ° of the coal contained in the starting material. This is then finely ground and soaked with a solution of ammonium phosphorus molybdate in ammonia water, so that the Coal absorbs o, oi ° / ° molybdic acid, and then dried.

An oil obtained through the pressure hydrogenation of hard coal, which is 50/0 boils up to 325 ° and contains 5 ° / ° asphalt, you put that much one in a colloid mill finely ground paste, consisting of tungstic acid and the same oil, to that all of the oil contains o, oi ° / ° tungstic acid.

This oil is mixed with the pretreated coal in the ratio i: z and preheated to 445 " together with hydrogen under 250 atm Carbon of the coal subjected to pressure hydrogenation is converted into liquid components consisting of gasoline and medium oil.

Claims (1)

PATENT CLAIM H :. Process for the production of valuable liquid products by treating solid carbonaceous materials mixed with C51 with hydrogen under pressure at elevated temperature in the presence of catalysts, characterized in that before the production of the mixture to be subjected to the reaction both the solid starting materials -with catalytically active material soaked or sprinkled, as well as the 01 to be added is mixed with catalysts.